WO2011065347A1 - Résine de polyamide copolymérisée, son procédé de fabrication, composition de résine et article moulé formé à partir de la résine de polyamide copolymérisée ou de la composition de résine - Google Patents

Résine de polyamide copolymérisée, son procédé de fabrication, composition de résine et article moulé formé à partir de la résine de polyamide copolymérisée ou de la composition de résine Download PDF

Info

Publication number
WO2011065347A1
WO2011065347A1 PCT/JP2010/070858 JP2010070858W WO2011065347A1 WO 2011065347 A1 WO2011065347 A1 WO 2011065347A1 JP 2010070858 W JP2010070858 W JP 2010070858W WO 2011065347 A1 WO2011065347 A1 WO 2011065347A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide resin
copolymerized polyamide
melting point
component
dicarboxylic acid
Prior art date
Application number
PCT/JP2010/070858
Other languages
English (en)
Japanese (ja)
Inventor
神田　智道
菊地　稔
克巳 篠原
英之 黒瀬
Original Assignee
三菱瓦斯化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to US13/512,214 priority Critical patent/US8895690B2/en
Priority to PH1/2012/501041A priority patent/PH12012501041A1/en
Priority to RU2012121824/04A priority patent/RU2565069C2/ru
Priority to KR1020127013181A priority patent/KR101845405B1/ko
Priority to CN201080053801.4A priority patent/CN102648232B/zh
Priority to EP10833193.5A priority patent/EP2505597B1/fr
Priority to JP2011543253A priority patent/JP5637144B2/ja
Publication of WO2011065347A1 publication Critical patent/WO2011065347A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention provides a copolymerized polyamide resin having excellent performance in all of mechanical properties, heat resistance properties, chemical physical properties and molding properties, and having very stable quality, a method for producing the same, a resin composition thereof, and the like It is related with the molded article which consists of. More specifically, a copolymerized polyamide resin comprising a diamine component comprising at least two components including a specific diamine component and a dicarboxylic acid component, and having very homogeneous and stable resin properties, its efficient production method, and resin composition
  • the present invention relates to a product and a molded product made of them.
  • Polyamide resins typified by nylon 6 and nylon 66 are excellent in toughness, chemical resistance, electrical properties, etc., and are widely used as molding materials in automobile parts, machine parts, electrical / electronic equipment parts and the like.
  • polyamides obtained from metaxylylenediamine and adipic acid hereinafter sometimes referred to as nylon MXD6
  • nylon MXD6 polyamides obtained from metaxylylenediamine and adipic acid
  • Nylon MXD6 has a slower crystallization speed than nylon 6 and nylon 66, so nylon MXD6 alone is difficult to crystallize in the mold during injection molding, making it difficult to thin-wall molding, or deformation of the resulting molded product And problems such as a decrease in mechanical strength are likely to occur. Therefore, in order to use nylon MXD6 as a molding material, nylon 66 or talc powder having a high crystallization speed is blended to increase the crystallization speed, or the mold temperature is increased to improve the moldability. There is a need (Patent Document 1). However, since the nylon 66 is blended, the water absorption rate is larger than that of the nylon MXD6 alone, and therefore, the mechanical strength is decreased due to water absorption.
  • a high crystallization rate copolymer polyamide is used as a main raw material of polyamide by using a mixture of metaxylylenediamine and paraxylylenediamine as a diamine component and adipic acid as a dicarboxylic acid component.
  • an inorganic filler with such a copolymerized polyamide (Patent Documents 2 and 3).
  • This technology facilitates thin-wall molding, which was difficult with conventional molding materials using nylon MXD6, and improved improvements such as shortening the molding cycle, lowering the mold temperature, and suppressing the deterioration of mechanical properties due to water absorption. It is done.
  • a general polyamide production method uses nylon salt or an aqueous solution thereof as a feedstock, and in a batch system, the aqueous nylon salt solution is heated under pressure in a single reaction tank, and polymerization is performed in a uniform phase while suppressing distillation of the diamine component. Then, after fixing the diamine component, the water vapor in the system is gradually released, and finally the pressure is reduced to normal pressure or reduced pressure to complete the polymerization. At this time, it is common to use an aqueous solution of about 50 wt% nylon salt as a feedstock, but a large amount of water and condensed water as a solvent must be removed.
  • Patent Document 4 as a polymerization method in which a nylon salt and an aqueous solution of a nylon salt are not used as a feedstock, a reaction is carried out by dropping a diamine component containing a small amount of water into a dicarboxylic acid component at a temperature of 220 ° C. or lower under normal pressure.
  • the reaction start temperature is set to be equal to or higher than the melting point of dicarboxylic acid, and the reaction system including the raw material mixture is brought into a substantially homogeneous molten state.
  • the reaction proceeds while raising the temperature so that it can be maintained, and before the reaction rate reaches 95%, the temperature of the reaction system is raised to a temperature that is 30 ° C. lower than the melting point of the copolyamide that generates the reaction system.
  • a method for producing a copolyamide by controlling the reaction temperature so that the reaction can proceed in a homogeneous system without losing the reaction is disclosed.
  • the above production method is characterized in that diamine is continuously added to the reaction system while maintaining the reaction system containing the generated oligoamide / polyamide in a homogeneous molten state. It does not need to be a pressure vessel.
  • this production method requires a time required for operations such as pressurization and pressure reduction of the reaction system, and a time required for distilling off water used as a solvent in the case of an aqueous solution method, as compared with the conventional polyamide production method.
  • the time required for polycondensation can be significantly shortened, and the amount of heat required for aqueous solution concentration is not required at all, and the amount that can be charged in one reaction is increased.
  • This is a highly advantageous method as a method for producing a copolymerized polyamide.
  • the production method has a problem in that the production and deposition of a polyamide having a high paraxylylenediamine composition locally becomes more apparent when a copolyamide containing paraxylylenediamine is produced.
  • the dicarboxylic acid evaporated from the molten dicarboxylic acid and deposited in the polymerization apparatus reacts with the evaporated diamine similarly to form a nylon salt or oligomer.
  • the salt of metaxylylenediamine and dicarboxylic acid has low solubility in water, so it is difficult to dissolve in the reflux of condensed water generated in the reaction.
  • Nylon salts are easily deposited selectively. The deposited nylon salt undergoes amidation as a solid, and becomes a high melting point oligomer insoluble in water.
  • the deposited oligomer If the deposited oligomer is dropped in the first half of the manufacturing process and mixed into the reaction solution, it can be homogenized by depolymerization with the reaction solution until the end of the reaction, but the viscosity increased when mixed in the second half of the manufacturing process. Since it is not sufficiently mixed with the reaction solution and cannot be completely depolymerized, it remains in the polyamide as a high melting point foreign matter. Moreover, the deposit which received the heat history for a long time by repeating the number of batches becomes a gel form insoluble in polyamide, and there is a risk of causing performance variation and deterioration.
  • the pipe and the condenser that lead the vapor mainly composed of condensed water generated by the polymerization reaction from the reaction tank to the condenser are the most deposited nylon salt or oligomer in the part of the polymerization equipment. These pipes and partial condensers are blocked, and continuous batch production cannot be performed.
  • control of the molar balance is very important in order to achieve a desired degree of polymerization. It is difficult to control the balance, and the method of adding the diamine component to the dicarboxylic acid component under normal pressure leaves many inconveniences for obtaining a homogeneous and good product.
  • Patent Document 6 discloses a method in which a total amount of diamine is added to dicarboxylic acid in a very short time and reacted under pressure. This method involves various disadvantages because the total amount of diamine is added in a very short time. In this method, it is necessary to take measures for avoiding foaming, liquid level fluctuation, solidification of the polymer due to latent heat of evaporation of the water, distillation of the monomer, etc. due to the condensed water generated in a large amount in a short time. In particular, a high pressure is required for the pressure, and in the process of decreasing the pressure in order to proceed with polymerization, it takes a long time to reduce the pressure while suppressing foaming.
  • Patent Document 7 discloses a method of lowering the paraxylylenediamine concentration in the diamine in the latter half of the reaction when the reaction is carried out by adding a diamine component containing metaxylylenediamine and paraxylylenediamine to adipic acid. ing. In this method, it is necessary to prepare diamines having different compositions, so that not only the number of equipment increases, but also switching operation of diamine to be added during the reaction becomes complicated and the operation becomes complicated, so it is difficult to say that it is an efficient method. .
  • the object of the present invention is to obtain a copolymer polyamide resin composed of a diamine component and a dicarboxylic acid component comprising at least two components including a paraxylylenediamine component, and the resin properties are very homogeneous and stable, and have mechanical properties and heat resistance properties.
  • Another object of the present invention is to provide a copolyamide resin for molding having excellent performance in both chemical physical properties and molding properties, a production method thereof, a resin composition, and a molded product comprising them.
  • a diamine component comprising at least two components containing at least 70 mol% of xylylenediamine containing at least 20 mol% of paraxylylenediamine and a linear aliphatic group having 6 to 18 carbon atoms.
  • a copolymer polyamide resin comprising a dicarboxylic acid component containing 70 mol% or more of a dicarboxylic acid is obtained by producing the copolymer polyamide under a condition that suppresses local generation of the copolyamide having an unduly high paraxylylenediamine composition ratio.
  • the present inventors have found that the polymerized polyamide resin has excellent performance in all of mechanical properties, heat resistance properties, chemical physical properties, and molding properties, and completed the present invention.
  • the present invention provides 70 mol% of a diamine component comprising at least two components including xylylenediamine containing 20 mol% or more of paraxylylenediamine and 70 mol% or more, and a linear aliphatic dicarboxylic acid having 6 to 18 carbon atoms.
  • a copolymerized polyamide resin comprising a dicarboxylic acid component as described above, which has 1000 / granular particles having a major axis of 50 ⁇ m or more containing a polyamide component whose melting point in differential scanning calorimetry (DSC) measurement is 20 ° C. or more higher than that of the copolymerized polyamide resin.
  • a copolymerized polyamide resin having a g or less A copolymerized polyamide resin composition comprising 100 parts by weight of the copolymerized polyamide resin and 0-30 parts by weight of talc and 10-150 parts by weight of an inorganic filler; Molded product obtained by molding the copolymerized polyamide resin, A diamine component consisting of at least two components containing 20 mol% or more of xylylenediamine and 70 mol% or more of xylylenediamine, and a dicarboxylic acid component containing 70 mol% or more of a linear aliphatic dicarboxylic acid having 6 to 18 carbon atoms And a polycondensation of a diamine component and a dicarboxylic acid component in the absence of a solvent using a batch reactor equipped with a condenser, The diamine component is continuously or intermittently added to the molten dicarboxylic acid component while maintaining the pressure at 1 MPaG or more and maintaining the temperature at which
  • the copolymerized polyamide resin obtained by the present invention has the following excellent effects.
  • (Ii) Nylon salts and oligomers in the reaction system are prevented from adhering to the reaction system, and because it is obtained by a production method that suppresses distilling of the diamine component, it is easy to control the molar balance, and the degree of polymerization is highly controlled. A homogeneous and good copolymerized polyamide resin is obtained.
  • dicarboxylic acid component used in the method according to the present invention examples include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; And aromatic dicarboxylic acids such as isophthalic acid and 2,6-naphthalenedicarboxylic acid, among which adipic acid or sebacic acid is preferred. These can be used alone or in combination.
  • the dicarboxylic acid component is preferably a dicarboxylic acid containing 70 mol% or more of adipic acid or sebacic acid, and more preferably 90 mol% or more.
  • the sulfur atom concentration is preferably 1 to 200 ppm, more preferably 10 to 150 ppm, and particularly preferably 20 to 100 ppm.
  • an increase in YI when a copolymerized polyamide resin is synthesized can be suppressed.
  • the increase in YI at the time of melt-molding the copolymerized polyamide resin can be suppressed, and the YI of the obtained molded product can be lowered.
  • the sebacic acid to be used preferably has a sodium atom concentration of 1 to 500 ppm, more preferably 10 to 300 ppm, and particularly preferably 20 to 200 ppm.
  • the reactivity when synthesizing the copolymerized polyamide resin is good, it is easy to control the molecular weight range, and the amount of the alkali metal compound to be blended for the purpose of adjusting the amidation reaction rate described later is used. Can be reduced.
  • when compounding a copolymerized polyamide resin and glass filler or the like it tends to be easy to suppress the generation of resin degradation products such as so-called spears that occur in the die.
  • Such sebacic acid is preferably derived from a plant. Since plant-derived sebacic acid contains sulfur compounds and sodium compounds as impurities, copolymer polyamide resins having plant-derived sebacic acid as a constituent unit have a low YI even without the addition of an antioxidant. The YI of the obtained molded product is also low. Moreover, it is preferable to use plant-derived sebacic acid without excessive purification of impurities. Since it is not necessary to purify excessively, it is advantageous in terms of cost.
  • the diamine component used in the method according to the present invention is a diamine containing xylylenediamine at 70 mol% or more, preferably 90 mol% or more.
  • 70 mol% or more of the xylylenediamine component it becomes possible to obtain excellent mechanical characteristics and heat resistance characteristics.
  • 20 mol% or more, preferably 30 mol% or more of the xylylenediamine used in the present invention is paraxylylenediamine.
  • the xylylenediamine is preferably composed of two components, metaxylylenediamine and paraxylylenediamine.
  • the amount of paraxylylenediamine in the xylylenediamine is preferably 20 to 90 mol%, more preferably 20 to 65.
  • the mol% is more preferably 30 to 50 mol%. It is preferable for the content of paraxylylenediamine in the diamine component to be in this range because it does not easily cause thermal deterioration due to the synthesis of the copolymerized polyamide resin or heating during molding, and molding becomes easy. If the paraxylylenediamine component is less than 20 mol%, the crystallization speed of the resulting copolymerized polyamide resin is low, which leads to deterioration of moldability, deformation due to poor crystallization of the molded product, and reduction of mechanical strength.
  • diamine components can be used as long as the effects of the present invention are not impaired.
  • diamine components aliphatic diamines such as tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 30 mol% of aromatic diamines such as metaphenylenediamine and paraphenylenediamine, and alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane in the total diamine It can be used in the following ranges.
  • the copolyamide resin molding component other than the diamine component and the dicarboxylic acid component is not particularly limited, but lactams such as caprolactam, valerolactam, laurolactam, undecalactam; 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.
  • lactams such as caprolactam, valerolactam, laurolactam, undecalactam; 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.
  • An aminocarboxylic acid etc. can be mentioned, These 1 type or 2 types or more may be included.
  • a phosphorus compound can be added to the copolymerized polyamide resin.
  • hypophosphorous acid compounds such as hypophosphorous acid and hypophosphite
  • phosphorous acid compounds such as phosphorous acid, phosphite and phosphorous acid ester
  • phosphoric acid compounds such as phosphoric acid, phosphate and phosphoric acid ester, etc.
  • hypophosphites include potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, manganese hypophosphite, nickel hypophosphite, cobalt hypophosphite and the like.
  • phosphites include potassium phosphite, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, nickel phosphite, cobalt phosphite and the like.
  • Phosphite esters include methyl phosphite, phosphite Examples include phosphoric acid ethyl ester, phosphorous acid isopropyl ester, phosphorous acid butyl ester, phosphorous acid hexyl ester, phosphorous acid isodecyl ester, phosphorous acid decyl ester, phosphorous acid stearyl ester, phosphorous acid phenyl ester, and the like.
  • Examples of the phosphate include potassium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate, manganese phosphate, nickel phosphate, and cobalt phosphate.
  • Examples of the phosphate ester include phosphoric acid methyl ester, phosphoric acid ethyl ester, phosphoric acid isopropyl ester, and phosphoric acid butyl ester. And hexyl phosphate, isodecyl phosphate, decyl phosphate, stearyl phosphate, and phenyl phosphate. These phosphoric acid antioxidants may be used alone or in combination.
  • Examples of the method for adding these phosphorus compounds include a method for adding to a diamine component or dicarboxylic acid component which is a raw material of the copolymerized polyamide resin, a method for adding during the reaction, etc., but the present invention is limited to these. is not. Further, in order to prevent the phosphorus compound from aggregating in the copolymerized polyamide resin or causing an abnormal reaction due to deterioration during heating, an alkali metal and an alkaline earth metal compound can be added together.
  • sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide and carbonic acid boric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, crotonic acid, valeric acid, caproic acid, isocaproic acid, enanthic acid, Caprylic acid, pelargonic acid, stearic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, hydrocinnamic acid, ⁇ -phenylbutyric acid, p-phenoxybenzoic acid, o-oxycinnamic acid, o- ⁇ -chlorophenylpropionic acid, m- Examples include alkali metal and alkaline earth metal compounds of chlorophenylpropionic acid, but are not limited to these compounds.
  • the copolymerized polyamide resin of the present invention has 1000 / g of granular material having a major axis of 50 ⁇ m or more containing a polyamide component whose melting point in the differential scanning calorimeter (DSC) measurement is 20 ° C. or more higher than that of the copolymerized polyamide resin.
  • the granular material having a major axis of 50 ⁇ m or more is 800 particles / g or less, more preferably, the granular material having a major axis of 50 ⁇ m or more is 600 particles / g or less.
  • the number of granules having a major axis of 50 ⁇ m or more containing a polyamide component 20 ° C. or higher higher than that of the copolymerized polyamide resin of the present invention is 1,000 / g or less, and the number of granules having a major axis of 50 to 99 ⁇ m is 500 / g or less. It is desirable that the number of granules having a size of 100 to 199 ⁇ m is 500 / g or less, and the number of granules having a major axis of 200 ⁇ m or more is 100 / g or less.
  • the method for evaluating the quantity of the granular material containing the polyamide component having a high melting point present in the copolymerized polyamide resin of the present invention is not particularly limited, but is 10 ° C. higher than the melting point of the copolymerized polyamide resin of the present invention.
  • a method of measuring a cast film obtained by melting at a high resin temperature using a CCD line sensor camera and image processing software can be exemplified.
  • polyamide synthesis and molding processes are handled in the temperature range from about the melting point to about + 20 ° C unless otherwise restricted, in order to sufficiently melt the polyamide and suppress thermal degradation.
  • a polyamide component having a high temperature of 20 ° C. or more is likely to be produced.
  • this high melting point polyamide is mixed, it remains in the copolymerized polyamide resin without melting during synthesis and molding.
  • This inhomogeneous polyamide can cause molded products with low mechanical performance and heat resistance due to the influence of the high melting point polyamide dispersed in the molded product. Have.
  • the method for evaluating the quantity and size of the high melting point granular material in the copolymerized polyamide resin of the present invention it is possible to cool and solidify the melted copolymerized polyamide resin in an amorphous state at the time of injection molding and extrusion molding in the prior art.
  • Set the mold and touch roll temperature to a low temperature create molded pieces, films, sheets, bottles, etc., and view the molded product visually or by image analysis with a CCD camera and image processing software.
  • the method of measuring the quantity and dimensions can be mentioned.
  • the granular material in the obtained molded product can be collected from the molded product by cutting or the like, and can be confirmed to be a high-melting-point foreign material by measuring the melting point with DSC.
  • the relative viscosity of the copolymerized polyamide resin of the present invention at 25 ° C. (96% concentrated sulfuric acid solution 1 g / 100 mL) is preferably 1.80 to 4.20, more preferably 1.90 to 3.50, It is preferably 1.95 to 3.00.
  • the relative viscosity of the copolymerized polyamide resin is less than 1.80, not only the mechanical strength of the molded article made of the copolymerized polyamide resin of the present invention is insufficient, but also water absorption resistance, chemical resistance, and heat aging. Since properties such as properties deteriorate, it is not preferable.
  • the relative viscosity of the copolymerized polyamide resin is 1.80 or more, the molded article made of the copolymerized polyamide resin of the present invention has sufficient mechanical strength, and water absorption resistance, chemical resistance, and heat aging resistance are also improved.
  • a copolymerized polyamide resin having a relative viscosity of 1.80 or more can be easily obtained by continuing the reaction until a predetermined relative viscosity is reached during melt polymerization.
  • the melt polymerization time reaction time
  • the polyamide molecules are damaged, or abnormal reactions such as non-linear molecular growth (three-dimensional polymerization) occur, and colored degradation products, gels, etc. are likely to be generated.
  • the relative viscosity is 4.20 or more, it is difficult to avoid the abnormal reaction.
  • melt viscosity becomes very high it is not preferable because molding processing becomes difficult.
  • Molded products made of copolymerized polyamide resins with many colored deterioration products and gels have low viscosity stability during abnormal thickening and melt retention, and not only the moldability is significantly deteriorated, but also water absorption resistance and chemical resistance. This is not preferable because various physical properties such as heat resistance and heat aging resistance are also deteriorated.
  • the copolymerized polyamide resin of the present invention uses a batch reaction tank equipped with a partial condenser, polycondenses a diamine component and a dicarboxylic acid component in the absence of a solvent, and the pressure in the reaction tank is 0.1 MPaG or more.
  • the diamine component is continuously or intermittently added to the molten dicarboxylic acid component while maintaining a temperature at which the entire reaction system can be maintained in a fluid state, and the gas phase temperature in the reaction vessel is maintained.
  • the batch-type reaction tank in the present invention is equipped with a stirrer and a partial condenser and has a pressure-resistant design.
  • the piping leading to the gas phase part of the reaction tank and the partial condenser is equipped with appropriate heat insulation or heating equipment such as a heat medium jacket.
  • the molar balance of charging is arbitrarily selected.
  • the method for adjusting the molar balance of charging is, for example, measuring a dicarboxylic acid component in a molten state with a melting tank and supplying it to a reaction tank, and then measuring the diamine component entering the storage tank with a mass measuring instrument.
  • the method of supplying a component to a reaction system can be illustrated.
  • a mass meter such as a load cell or a balance can be suitably used.
  • a dicarboxylic acid component is charged into a reaction tank, and then the pressure in the reaction tank is increased to a set pressure of 0.1 MPaG or higher, and the pressure of 0.1 MPaG or higher is maintained.
  • the reaction tank is sufficiently replaced with an inert gas such as nitrogen in advance before the dicarboxylic acid component is charged into the reaction tank.
  • the dicarboxylic acid is melted, it is preferably performed in an inert gas atmosphere.
  • the dicarboxylic acid component is heated above its melting point in the reaction tank to be in a molten state, it is heated in a dedicated melting tank different from the reaction tank to be in a molten state and then charged into the reaction tank in a molten state. Either method is acceptable. From the viewpoint of increasing the utilization efficiency of the reaction tank, it is preferable to use a dedicated melting tank.
  • the time of the step of pressurizing the reaction tank to the set pressure only needs to reach the set pressure before the addition of the diamine component to the dicarboxylic acid component in the reaction tank is started. After reaching the set pressure, it is desirable to control the pressure in the reaction tank to be constant at the set pressure.
  • the pressure fluctuation during the reaction changes the saturated water vapor temperature and the linear velocity of the gas flowing in the partial condenser, so that the separation capacity of the condensed water and the reactive raw material in the partial condenser is reduced, and the reaction raw material, particularly the reaction of the diamine component. Distilling out of the system is unavoidable and it becomes difficult to control the molar balance.
  • the pressurization in the reaction vessel may be performed by an inert gas such as nitrogen or water vapor.
  • the set pressure is preferably selected so that the saturated water vapor temperature at the pressure in the reaction vessel during diamine addition is 150 ° C. or lower.
  • the required pressure varies depending on the diamine component and dicarboxylic acid component to be used, but generally it is preferably in the range of 0.1 to 0.4 MPaG.
  • the diamine component is continuously or intermittently added to the dicarboxylic acid component while maintaining the temperature at which the entire reaction system can be maintained in a fluid state while maintaining the pressure constant.
  • the dicarboxylic acid is preferably heated to a temperature of 150 ° C. or higher, which is the temperature at which the amidation reaction proceeds, and the oligomer and / or low molecular weight polyamide produced as an intermediate
  • the temperature of the reaction system is set to a temperature at which the reaction system can maintain a fluid state.
  • the reaction is usually performed at a temperature selected from 180 to 310 ° C, preferably from 180 to 290 ° C.
  • the specific diamine component addition operation involves stirring the dicarboxylic acid component in a molten state in the reaction vessel, adding the diamine component continuously or intermittently, and sequentially raising the temperature of the reaction mixture. And maintained at a temperature at which the entire reaction system can maintain a fluid state.
  • the addition rate of the diamine component is adjusted as appropriate, and the temperature of the reaction mixture at the end of the addition is above the melting point of the copolymerized polyamide resin, And it is preferably less than (melting point + 35 ° C.), more preferably less than (melting point + 15 ° C.), more desirably (melting point + 5 ° C.) or more and less than (melting point + 10 ° C.).
  • the melting point in the present invention refers to an endothermic peak temperature due to the heat of crystal fusion observed by a differential scanning calorimeter (DSC) measurement or the like, and the melting point of the reaction system can be confirmed by appropriately measuring by DSC or the like.
  • DSC differential scanning calorimeter
  • the gas phase temperature in the reaction vessel is set to be equal to or higher than the melting point of the nylon salt made of the raw material until 80% of the total amount of the diamine component is added.
  • the gas phase temperature in the reaction vessel is raised before 70%, more preferably 60%, of the total amount of diamine components is added.
  • diamine or dicarboxylic acid vapor is present in addition to the condensed water generated in the gas phase of the reaction tank. Since xylylenediamine and dicarboxylic acid have a higher dew point than water, they easily condense in the gas phase of the apparatus, and form a nylon salt at the condensed position on the apparatus wall surface. When the gas phase temperature is below the melting point of the nylon salt, the nylon salt is solid and deposits on the wall surface of the gas phase of the device, and amidation proceeds in the deposited state. To do.
  • nylon salts have some solubility in water, so increasing the amount of condensed water reflux in the production process may have a certain effect on the suppression of nylon salt deposition, but is necessary for re-evaporation of the reflux liquid.
  • a heating time is required for that purpose, and local heating for giving excessive heat transfer causes heat degradation of the polyamide reaction solution.
  • the water solubility of the nylon salt is low, so that the effect cannot be sufficiently obtained, and when the amount of the reflux water is increased, the reflux liquid temperature itself also decreases. Since the solubility of the nylon salt is further lowered, it is difficult to actually obtain the intended effect.
  • the reflux water temperature is increased by pressurizing the inside of the reaction tank, so that the solubility of nylon salt in water also increases, but the water composition in the reflux liquid is It was low and its effect alone was insufficient to dissolve all the nylon salt in the water in the reflux and wash it off.
  • the gas phase temperature in the reaction vessel is set to be equal to or higher than the melting point of the nylon salt made of the raw material before 80% of the total amount of diamine components is added.
  • the melting point of the nylon salt can be determined by the method described below.
  • the gas phase temperature exceeds the melting point of the nylon salt after the addition of 80%, some effect can be obtained during the diamine addition process, but the liquid viscosity increases as the polycondensation reaction proceeds. It is difficult to homogenize, and it is not preferable because it does not react and is likely to be mixed in as a high melting point polyamide. Further, after the diamine dropping step, the washing effect by the reflux liquid is not obtained, and the viscosity of the liquid becomes considerably high, so that it is difficult to avoid mixing the high melting point polyamide in the copolymerized polyamide resin.
  • the condensed water produced as the reaction proceeds is distilled out of the reaction system through a partial condenser and further a cooler.
  • the internal temperature of the divider is preferably controlled to 150 ° C. or less.
  • a diamine component, a dicarboxylic acid component, and the like distilled out of the reaction system as steam together with condensed water are separated from water vapor by a partial condenser and returned to the reaction tank again.
  • Continuous production in which the internal temperature of the partial condenser exceeds 150 ° C. accumulates polyamide oligomers that are not dissolved in the condensed water inside the partial condenser. Each time the number of batches is increased, the amount of polymer inside the condensing device increases, causing clogging inside the condensing device and making continuous batch production difficult.
  • the internal temperature of the partial condenser is lower than 150 ° C, and is controlled at a temperature in the range of the saturated water vapor temperature to + 5 ° C. It is desirable to do.
  • the reflux amount in the partial condenser is decreased, and therefore, it is not preferable because the cleaning effect of the nylon salt or oligomer adhering to the partial condenser cannot be expected.
  • the internal temperature of the partial condenser when the internal temperature of the partial condenser is lower than the saturated water vapor temperature, the amount of reflux of the condensed water increases, and the amount of condensed water that has returned to the reaction system decreases the temperature of the reaction mixture. The temperature of the gas phase part is also reduced, and it becomes difficult to avoid the formation of nylon salt, oligomer deposition and the incorporation of high melting point polyamide into the copolymerized polyamide resin, and the polymer due to the latent heat of vaporization of water. This is not preferable because of the risk of solidifying and precipitating and maintaining the molten state.
  • it is desirable to appropriately select the pressure of the reaction vessel For example, when the predetermined pressure in the reaction vessel is 0.3 MPaG, the internal set temperature of the partial condenser is adjusted to 143 ° C. to 148 ° C.
  • the pressure in the reaction vessel is reduced to atmospheric pressure or lower. At that time, it is preferable to lower the pressure to a reduced pressure, distill off the water vapor present in the gas phase portion outside the reaction system, and further increase the degree of polymerization using amidation equilibrium. During the pressure drop, the entire reaction system is maintained at a temperature at which it can maintain a fluid state. In the process of lowering the pressure in the reaction vessel, a pressure reduction rate at which foaming of the produced polyamide is suppressed is selected. Although depending on the scale and pressure of the reaction vessel, it is preferable to reduce the pressure in the range of 0.1 to 0.6 MPa / hour.
  • the reaction tank is maintained at a set pressure for 5 minutes or more and 3 hours or less while maintaining a temperature at which the entire reaction system can maintain a fluid state. Preferably, it is 10 minutes or more and 1 hour or less.
  • the reaction tank In the initial stage of the addition of the diamine component, there are a considerable excess of carboxyl groups relative to the diamine component, and the reaction rate of the diamine component, that is, the immobilization rate is extremely fast. However, a considerable amount of carboxyl groups is consumed at the end of the addition, and the immobilization rate of the diamine component is extremely slow compared to the initial stage of addition.
  • the increase in the degree of polymerization lowers the stirring efficiency of the reaction mixture, which is further disadvantageous for immobilizing the diamine component.
  • the diamine component that has not been immobilized is present in the reaction mixture or in the gas phase in the reaction system, or the condensed diamine component is added to the reaction mixture again. After completion of the addition of the diamine component, such a diamine component is fixed by holding at a set pressure for at least 5 minutes, and the molar balance of the preparation is accurately reproduced in the polyamide molar balance.
  • maintained by setting pressure depends on the fixation
  • holding more than necessary after immobilization of the diamine component is meaningless and is undesirable because it causes inconveniences such as an increase in heat history and a decrease in productivity. Accordingly, the holding time is generally preferably within 3 hours.
  • the reaction tank When the obtained polyamide is discharged from the reaction tank after the pressure drop, the reaction tank is usually pressurized. In this case, it is preferable to use an inert gas such as nitrogen. According to the present invention, since there is little adhesion of nylon salt or oligomer in the reaction tank after discharge, the reaction of the next batch can be continued, so that continuous batch production is possible.
  • a polyamide having a higher molecular weight can be produced by performing solid phase polymerization using the polyamide obtained by the present invention as a raw material and further proceeding with the polymerization. Further, the polyamide obtained by the present invention can be supplied to a continuous polymerization machine in a molten state, and the polymerization can be further advanced to produce a higher molecular weight polyamide.
  • the copolymerized polyamide resin composition of the present invention is obtained by blending the copolymerized polyamide resin with talc and an inorganic filler, and the inorganic filler to be used is generally used for this type of composition.
  • the inorganic filler to be used is generally used for this type of composition.
  • the blending ratio of the inorganic filler is preferably 10 to 150 parts by weight with respect to 100 parts by weight of the copolymerized polyamide resin in consideration of mechanical performance and the like.
  • the fibrous filler glass fibers, potassium titanate or calcium sulfate whiskers, carbon fibers, alumina fibers, and the like can be used.
  • the powdery packing preferably has a particle size of 100 ⁇ m or less, more preferably 80 ⁇ m or less, carbonates such as kaolinite, silica, calcium carbonate, magnesium carbonate, sulfuric acid such as calcium sulfate, magnesium sulfate, etc. Salts, sulfides and metal oxides can be used.
  • the talc blended in the copolymerized polyamide resin composition of the present invention is for further promoting crystallization.
  • the talc to be used has a particle size of preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and is blended at a ratio of 30 parts by weight or less with respect to 100 parts by weight of the copolymerized polyamide resin.
  • the blending ratio of talc exceeds 30 parts by weight with respect to 100 parts by weight of the copolymerized polyamide resin, it causes adverse effects such as a decrease in fluidity of the resin during molding and a decrease in mechanical performance of the obtained molded product. It is not preferable.
  • copolymer polyamide resin composition of the present invention can be blended with other resins such as nylon 6, nylon 66, nylon 6,66, polyester, olefin and the like within a range not impairing the purpose, and kaolinite, mica, montmorillonite can be blended.
  • Organized plate-like inorganic fillers impact modifiers such as various elastomers, crystal nucleating agents; lubricants such as fatty acid amides and fatty acid metal salt compounds; copper compounds, organic or inorganic halogen compounds, hinders Antioxidants such as dophenols, hindered amines, hydrazines, sulfur compounds, phosphorus compounds; heat stabilizers, anti-coloring agents, UV absorbers such as benzotriazoles, release agents, plasticizers, colorants, Gelling of additives such as flame retardants, compounds containing cobalt metal, a compound that imparts oxygen scavenging ability, and copolymerized polyamide resins It may be added an additive of an alkali compound such as for the purpose of stopping.
  • lubricants such as fatty acid amides and fatty acid metal salt compounds
  • the molded article of the present invention is formed by molding the copolymerized polyamide resin or copolymerized polyamide resin composition of the present invention, and molding methods such as injection molding, blow molding, extrusion molding, compression molding, stretching, and vacuum molding are applicable.
  • This molded product can be molded not only into a molded body as an engineering plastic, but also in the form of a film, a sheet, a hollow container, a fiber, a tube, etc., and can be suitably used for industrial materials, industrial materials, household goods, etc. I can do it.
  • Terminal carboxyl group concentration 0.3 to 0.5 g of the copolymerized polyamide resin was precisely weighed and dissolved in 30 cc of benzyl alcohol with stirring at 160 to 180 ° C. in a nitrogen stream. After completely dissolving, it was cooled to 80 ° C. or lower under a nitrogen stream, 10 cc of methanol was added with stirring, and neutralization titration with an N / 100 aqueous sodium hydroxide solution was performed.
  • Number average molecular weight 2 / ([NH 2 ] + [COOH]) ([NH 2 ] represents the terminal amino group concentration ( ⁇ eq / g), and [COOH] represents the terminal carboxyl group concentration ( ⁇ eq / g).)
  • nylon salt as copolymer polyamide resin raw material and melting point measurement
  • diamine and dicarboxylic acid molar ratio 1: 1
  • the completely dissolved aqueous solution was transferred to an evaporator, and water was distilled off under reduced pressure in a hot water bath.
  • the obtained nylon salt was vacuum-dried at 90 ° C. for one day and night, and the melting point was measured by DSC. When two or more melting peaks occurred, the peak temperature on the high melting point side was adopted as the nylon salt melting point.
  • Example 1 For the synthesis of the copolymerized polyamide resin, a 50 liter stainless steel reaction with an oil jacket equipped with a partial condenser, a total condenser, a stirrer, a nitrogen gas introduction pipe and a diamine dropping port through which temperature-controlled oil flows. A tank was used. In order to control the gas phase temperature of the reaction tank, an electric heater heating device with a temperature control function is installed on the outer wall surface of the tank other than the oil jacket of the reaction tank. During the synthesis of the copolymerized polyamide resin, the temperature of the gas-phase wall surface in the apparatus was adjusted to 230 ° C.
  • Aipic acid (purity: 99.85 wt%) 15.000 kg precisely weighed in the reaction vessel was charged and sufficiently purged with nitrogen. A heating medium at 300 ° C. was passed through the jacket to start the temperature rise, and adipic acid was dissolved while stirring to make it flow. Meanwhile, supply of nitrogen was started in the reaction tank, and the pressure in the reaction tank was increased to 0.4 MPaG. When heated to 190 ° C., while stirring molten adipic acid, 13.909 kg of mixed xylylenediamine (purity: 99.95 wt%) containing 70 mol% of metaxylylenediamine and 30 mol% of paraxylylenediamine was added. It was added dropwise over time.
  • the temperature is continuously raised and the heating is adjusted so that the internal temperature at the end of dropping of the mixed xylylenediamine is 265 ° C.
  • the pressure in the reaction vessel is controlled at 0.4 MPaG
  • the temperature was controlled at 150 ° C. and was removed from the reaction system through a condenser and a condenser.
  • the temperature in the gas phase of the reaction vessel also increased as needed, and when the 70% of the total amount of diamine was added dropwise, the melting point of the nylon salt composed of mixed xylylenediamine and adipic acid was 227 ° C or higher.
  • the temperature rising rate was raised at 0.2 ° C./min with continued stirring, and the pressure in the reaction vessel was maintained at 0.4 MPaG for 15 minutes. Further, the pressure was reduced to 80 kPaA at a rate of 0.6 MPa / hour and held at 80 kPaA for 5 minutes. Thereafter, the heating was stopped, the pressure was increased with nitrogen, the strand was taken out from the nozzle at the bottom of the reaction tank, cooled with water, and then cut into pellets to obtain a copolymerized polyamide resin in an amorphous state.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.12, a number average molecular weight of 15,800, a copolymerized polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of ⁇ 5, and a melting point of 258 ° C. It was.
  • the relative viscosity was 2.06 to 2.14
  • the number average molecular weight was 14,800 to 16,000
  • the molar balance was 0.993 to 0.995
  • YI Was stable at -6 to -3.
  • the obtained copolymerized polyamide resin was formed into a film and the granular material was measured.
  • the total amount of the granular material of 50 ⁇ m or more was 104 / g, 50 to 99 ⁇ m was 53 / g, 100 to 199 ⁇ m was 42 / g, 200 ⁇ m.
  • the above was 9 pieces / g, the number of granular materials was very small, and the film appearance was good.
  • the melting point of the granular part was cut out, the melting point of 282 ° C. was included in addition to the copolymer polyamide resin melting point of 258 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin and performance was evaluated.
  • the bending elastic modulus was 4280 MPa, the standard deviation was 18, the bending strength was 174 MPa, the standard deviation was 1, The deformation temperature was 174 ° C., the standard deviation was 1, and the mechanical properties and heat resistance were excellent, and the quality was very stable.
  • Example 2 The apparatus was the same as in Example 1 except that the pressure in the reaction vessel was 0.2 MPaG, and the distilled water was removed from the reaction system through a condenser and a condenser whose internal temperature was controlled at 120 to 124 ° C.
  • Copolyamide resin was synthesized under the same conditions.
  • the obtained copolymer polyamide resin had a relative viscosity of 2.09, a number average molecular weight of 15,300, a copolymer polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of ⁇ 4, and a melting point of 258 ° C. It was.
  • the above was 15 pieces / g, the number of granular materials was very small, and the film appearance was good.
  • the melting point of the granular part was cut out, the melting point of 280 ° C. was included in addition to the copolymer polyamide resin melting point of 258 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin and performance was evaluated.
  • the bending elastic modulus was 4265 MPa, the standard deviation was 15, the bending strength was 174 MPa, the standard deviation was 1, The deformation temperature was 175 ° C., the standard deviation was 1, and the mechanical properties and heat resistance were excellent, and the quality was very stable.
  • Example 3 Using mixed xylylenediamine (purity: 99.95 wt%) containing 60 mol% of metaxylylenediamine and 40 mol% of paraxylylenediamine, and continuously raising the temperature of the reaction solution during the diamine dropping step The internal temperature at the end of the dropwise addition of xylylenediamine was 275 ° C. During this time, the wall surface of the gas phase of the apparatus was adjusted to 240 ° C, and the temperature of the gas phase of the reaction vessel was dropped by 70% of the total amount of diamine added.
  • a copolymerized polyamide resin was synthesized under the same conditions as in Example 1 except that the melting point of the nylon salt composed of mixed xylylenediamine and adipic acid was controlled to 230 ° C. or higher.
  • the obtained copolymer polyamide resin had a relative viscosity of 2.10, a number average molecular weight of 15500, a copolymer polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of -3, and a melting point of 269 ° C. It was.
  • the above was 26 pieces / g, the number of granular materials was very small, and the film appearance was good.
  • the melting point of the granular part was cut out, the melting point of 293 ° C. was included in addition to the copolymer polyamide resin melting point of 269 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin and performance was evaluated.
  • the bending elastic modulus was 4270 MPa, the standard deviation was 23, the bending strength was 172 MPa, the standard deviation was 1, The deformation temperature was 179 ° C., the standard deviation was 2, and the mechanical characteristics and heat resistance characteristics were excellent, and the quality was very stable.
  • Example 4 Mixed xylylenediamine (purity: 99.95 wt%) containing 50 mol% metaxylylenediamine and 50 mol% paraxylylenediamine, and the reaction solution was continuously heated and mixed during the diamine dropping step.
  • the internal temperature at the end of the dropwise addition of xylylenediamine was 285 ° C.
  • the wall surface of the gas phase of the apparatus was adjusted to 250 ° C, and the temperature of the gas phase of the reaction vessel was dropped by 75% of the total amount of diamine added.
  • a copolymerized polyamide resin was synthesized under the same conditions as in Example 1 except that the melting point of the nylon salt composed of mixed xylylenediamine and adipic acid was controlled to 238 ° C. or higher.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.11, a number average molecular weight of 15,700, a molar balance (diamine / dicarboxylic acid) of the copolymerized polyamide resin of 0.993, YI of ⁇ 1, and a melting point of 278 ° C. It was.
  • the above was 35 pieces / g, and there were very few granular materials and the film external appearance was also favorable.
  • the melting point of the granular part was cut out, the melting point of 302 ° C. was included in addition to the copolymer polyamide resin melting point of 278 ° C.
  • a molded piece was prepared using the obtained copolymer polyamide resin, and performance was evaluated.
  • the bending elastic modulus was 4263 MPa, the standard deviation was 28, the bending strength was 171 MPa, the standard deviation was 2, The deformation temperature was 189 ° C., its standard deviation was 2, and it was excellent in mechanical characteristics and heat resistance characteristics, and the quality was very stable.
  • Example 5 As dicarboxylic acid component, 15.135 kg of sebacic acid (purity: 99.70 wt%, sulfur atom concentration 30 ppm, sodium atom concentration 54 ppm) was charged, and diamine components were metaxylylenediamine 70 mol% and paraxylylenediamine 30 mol%. 10.100 kg of mixed xylylenediamine (purity: 99.95 wt%) contained was dropped, and the reaction solution was continuously heated during the diamine dropping step so that the internal temperature at the end of the diamine dropping was 250 ° C.
  • sebacic acid purity: 99.70 wt%, sulfur atom concentration 30 ppm, sodium atom concentration 54 ppm
  • diamine components metaxylylenediamine 70 mol% and paraxylylenediamine 30 mol%.
  • 10.100 kg of mixed xylylenediamine (purity: 99.95 wt%) contained was dropped, and the reaction solution was continuously heated during the diamine dropping step so that the internal
  • the temperature of the gas phase wall of the apparatus was adjusted to 230 ° C., and when the temperature of the gas phase of the reaction vessel was dropped by 35% of the total amount of diamine added, nylon consisting of mixed xylylenediamine and sebacic acid
  • the copolymerized polyamide resin was synthesized under the same conditions as in Example 1 except that the melting point of the salt was controlled to 191 ° C or higher. It was carried out.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.05, a number average molecular weight of 14900, a copolymerized polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of ⁇ 5, and a melting point of 214 ° C. It was.
  • the relative viscosity was 2.00 to 2.13
  • the number average molecular weight was 14200 to 15900
  • the molar balance was 0.993 to 0.995
  • YI was ⁇ 7 to It was stable at -3.
  • the obtained copolymerized polyamide resin was formed into a film and the granular material was measured.
  • the total amount of the granular material of 50 ⁇ m or more was 198 / g, 50-99 ⁇ m was 102 / g, 100-199 ⁇ m was 75 / g, 200 ⁇ m.
  • the above was 21 pieces / g, and there were very few granular materials and the film external appearance was also favorable.
  • the melting point of the granular part was cut out, the melting point of 250 ° C. was included in addition to the copolymer polyamide resin melting point of 214 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin, and the performance was evaluated.
  • the flexural modulus was 2920 MPa
  • the standard deviation was 14
  • the flexural strength was 135 MPa
  • the standard deviation was 1
  • the deformation temperature was 145 ° C.
  • the standard deviation was 2, and the quality was very stable.
  • Example 6 The mixed xylylenediamine (purity: 99.95 wt%) containing 60 mol% metaxylylenediamine and 40 mol% paraxylylenediamine as the diamine component was used. The temperature was adjusted to °C, and when the temperature of the gas phase part of the reaction vessel was dropped 40% of the total amount of diamine added, the temperature was controlled to a melting point of 197 ° C. or higher of the nylon salt composed of mixed xylylenediamine and sebacic acid. 5 was synthesized under the same conditions using the same apparatus as in No. 5.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.07, a number average molecular weight of 15100, a copolymerized polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of ⁇ 5, and a melting point of 223 ° C. It was.
  • the relative viscosity was 2.04 to 2.10
  • the number average molecular weight was 14700 to 15500
  • the molar balance was 0.993 to 0.995
  • the YI was ⁇ 7 to It was stable at -3.
  • the obtained copolymerized polyamide resin was formed into a film and the granular material was measured.
  • the total amount of granular material of 50 ⁇ m or more was 217 / g, 50-99 ⁇ m was 114 / g, 100-199 ⁇ m was 79 / g, 200 ⁇ m.
  • the above was 24 pieces / g, and there were very few granular materials and the film external appearance was also favorable.
  • the melting point of the granular part was cut, the melting point of 260 ° C. was included in addition to the copolymer polyamide resin melting point of 223 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin and performance was evaluated.
  • the bending elastic modulus was 2900 MPa, the standard deviation was 12, the bending strength was 134 MPa, the standard deviation was 1, The deformation temperature was 152 ° C., the standard deviation was 2, and the quality was very stable.
  • Example 7 As the diamine component, mixed xylylenediamine (purity: 99.95 wt%) containing 40 mol% metaxylylenediamine and 60 mol% paraxylylenediamine was used. The temperature was adjusted to °C, and when the temperature of the gas phase part of the reaction vessel was dropped to 50% of the total amount of diamine added, the temperature was controlled to be the melting point of the nylon salt composed of mixed xylylenediamine and sebacic acid at 202 °C or higher. 5 was synthesized under the same conditions using the same apparatus as in No. 5.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.11, a number average molecular weight of 15600, a molar balance (diamine / dicarboxylic acid) of the copolymerized polyamide resin of 0.994, YI of ⁇ 4, and a melting point of 242 ° C. It was.
  • the relative viscosity was 2.05 to 2.16
  • the number average molecular weight was 14600 to 16100
  • the molar balance was 0.993 to 0.995
  • the YI was ⁇ 6 to -2 was stable.
  • the obtained copolymerized polyamide resin was formed into a film and the granular material was measured.
  • the total amount of granular material of 50 ⁇ m or more was 225 / g, 50-99 ⁇ m was 120 / g, 100-199 ⁇ m was 83 / g, 200 ⁇ m.
  • the above was 22 pieces / g, and there were very few granular materials and the film external appearance was also favorable.
  • the melting point of the granular part was cut, the melting point of 281 ° C. was included in addition to the copolymer polyamide resin melting point of 242 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin and performance was evaluated.
  • the bending elastic modulus was 2930 MPa
  • the standard deviation was 15, the bending strength was 136 MPa
  • the standard deviation was 1
  • the deformation temperature was 170 ° C.
  • the standard deviation was 1, and the quality was very stable.
  • Example 8> As the diamine component, mixed xylylenediamine (purity: 99.95 wt%) containing 20 mol% of metaxylylenediamine and 80 mol% of paraxylylenediamine was used. The temperature of the reactor was adjusted to °C, and when the temperature of the gas phase part of the reaction vessel was dropped 55% of the total amount of diamine added, the melting point of the nylon salt composed of mixed xylylenediamine and sebacic acid was controlled to be 207 ° C or higher. 5 was synthesized under the same conditions using the same apparatus as in No. 5.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.10, a number average molecular weight of 15500, a copolymerized polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of ⁇ 4, and a melting point of 263 ° C. It was.
  • the relative viscosity was 2.04 to 2.14
  • the number average molecular weight was 14400 to 16000
  • the molar balance was 0.993 to 0.995
  • the YI was ⁇ 6 to -2 was stable.
  • the obtained copolymerized polyamide resin was made into a film and the granular material was measured.
  • the total amount of the granular material of 50 ⁇ m or more was 283 / g, 50 to 99 ⁇ m was 145 / g, 100 to 199 ⁇ m was 112 / g, 200 ⁇ m.
  • the above was 26 pieces / g, the number of granular materials was very small, and the film appearance was good.
  • the melting point of the granular part was cut, the melting point of 292 ° C. was included in addition to the copolymer polyamide resin melting point of 263 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin, and the performance was evaluated.
  • the bending elastic modulus was 2950 MPa, the standard deviation was 12, the bending strength was 135 MPa, the standard deviation was 1, The deformation temperature was 191 ° C., the standard deviation was 2, and the quality was very stable.
  • Example 1 The apparatus was the same as in Example 3 except that the pressure in the reaction vessel was normal and the distilled water was removed out of the reaction system through a condenser and a condenser whose internal temperature was controlled at 100 to 104 ° C. A copolymerized polyamide resin was synthesized under the same conditions. Since no increase in viscosity was observed up to the stirring torque corresponding to the predetermined molecular weight, the reaction was continued for 30 minutes after starting the pressure reduction to obtain a copolymerized polyamide resin.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.01, a number average molecular weight of 14300, a copolymerized polyamide resin molar balance (diamine / dicarboxylic acid) of 0.988, YI of ⁇ 1, and a melting point of 269 ° C. , Relative viscosity, number average molecular weight, and molar balance were low.
  • the total amount of the granular material of 50 ⁇ m or more was 3230 particles / g, 50 to 99 ⁇ m was 1592 particles / g, 100 to 199 ⁇ m was 1386 particles / g, When the thickness was 200 ⁇ m or more, 252 particles / g, the number of granular materials was very large, and the appearance of the film was large and uneven.
  • the melting point of the granulated part was measured, the melting point of 300 ° C. was included in addition to the copolymer polyamide resin melting point of 269 ° C. A molded piece was prepared using the obtained copolymerized polyamide resin and performance was evaluated.
  • the bending elastic modulus was 4246 MPa, the standard deviation was 94, the bending strength was 172 MPa, the standard deviation was 7, The deformation temperature was 183 ° C., the standard deviation was 9, the mechanical characteristics and the heat resistance were highly variable, and the quality was unstable.
  • Example 2 A copolymerized polyamide resin was synthesized in the same manner as in Example 3 except that the reaction vessel gas phase part wall surface was not heated.
  • the temperature of the gas phase is 208 ° C. at the time of dropping 80% of the total amount of diamine, 227 ° C. at the end of dropping, and the melting point of the nylon salt composed of mixed xylylenediamine and adipic acid is 230 ° C. or lower, and keeps 0.4 MPa thereafter. It became 230 degreeC or more inside.
  • the obtained copolymer polyamide resin had a relative viscosity of 2.09, a number average molecular weight of 15,300, a copolymer polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of ⁇ 6, and a melting point of 269 ° C. It was.
  • the relative viscosity was 2.07 to 2.14
  • the number average molecular weight was 14,900 to 16,000
  • the molar balance was 0.993 to 0.995
  • YI Was stable at -7 to -3.
  • the total amount of particulate matter of 50 ⁇ m or more was 1148 pieces / g, 50 to 99 ⁇ m was 572 pieces / g, 100 to 199 ⁇ m was 493 pieces / g, When the particle size was 200 ⁇ m or more, the number was 83 pieces / g, and there were many granular materials, and the film appearance was large and uneven.
  • the melting point of the granular part was cut, the melting point of 290 ° C. was included in addition to the copolymer polyamide resin melting point of 269 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin, and the performance was evaluated.
  • the bending elastic modulus was 4268 MPa
  • the standard deviation was 51
  • the bending strength was 173 MPa
  • the standard deviation was 4
  • the deformation temperature was 184 ° C.
  • the standard deviation was 4, the variation in mechanical properties and heat resistance was large, and the quality was unstable.
  • Adipic acid (purity: 99) was placed in a 50 liter stainless steel reaction tank with an oil jacket equipped with a partial condenser, a full condenser, a stirrer, a nitrogen gas inlet tube and a diamine dropping port through which temperature-controlled oil flows. .85 wt%) 10.000 kg, mixed xylylenediamine (purity: 99.95 wt%) 9.270 kg containing metaxylylenediamine 60 mol% and paraxylylenediamine 40 mol%, and distilled water 19 kg, fully nitrogen-substituted did. While stirring the contents with the apparatus sealed, the temperature was raised to 207 ° C.
  • the resulting copolymerized polyamide resin had a relative viscosity of 2.08, a number average molecular weight of 15100, a copolymerized polyamide resin molar balance (diamine / dicarboxylic acid) of 0.994, YI of -3, and a melting point of 269 ° C. It was.
  • the relative viscosity was 2.04 to 2.16
  • the number average molecular weight was 14,700 to 16,300
  • the molar balance was 0.993 to 0.995
  • YI Was stable at -6 to -1.
  • the total amount of the granular material of 50 ⁇ m or more was 1,422 particles / g, 50-99 ⁇ m was 721 particles / g, 100-199 ⁇ m was 610 particles / g,
  • the particle size was 200 ⁇ m or more, the number of particles was 91 pieces / g, and there were many granular materials, and the film appearance was uneven and the film was poor.
  • the melting point of the granular part was cut out, the melting point of 295 ° C. was included in addition to the copolymerized polyamide resin melting point of 269 ° C.
  • a molded piece was prepared using the obtained copolymerized polyamide resin, and the performance was evaluated.
  • the bending elastic modulus was 4251 MPa, the standard deviation was 65, the bending strength was 173 MPa, the standard deviation was 4, The deformation temperature was 173 ° C. and the standard deviation was 4.
  • the mechanical characteristics and the heat resistance characteristics varied greatly, and the quality was unstable.
  • the copolymerized polyamide resin obtained by the present invention has excellent mechanical properties, heat resistance properties, chemical physical properties, and molding properties, and has a very stable quality, so that it is a molded product and film. It is suitably used in a wide range of fields such as sheet and fiber.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une résine de polyamide copolymérisée pour moulage, qui est composée de : un composant diamine qui est composé d'au moins deux composants contenant une quantité supérieure ou égale à 70 % en moles de xylylène diamine qui contient une quantité supérieure ou égale à 20 % en moles de para-xylylène diamine ; et un composant acide dicarboxylique qui contient une quantité supérieure ou égale à 70 % en moles d'un acide dicarboxylique aliphatique linéaire de 6 à 18 atomes de carbone. La résine de polyamide copolymérisée contient des matériaux granulaires, qui ont chacun une longueur supérieure ou égale à 50 µm, et contient un composant polyamide qui a un point de fusion supérieur de 20 °C ou plus à celui de la résine de polyamide copolymérisée tel que mesuré par un calorimètre à balayage différentiel, avec une densité inférieure ou égale à 1 000 pièces/g. La résine de polyamide copolymérisée présente des propriétés de résine très uniformes et stables, tout en présentant d'excellentes caractéristiques mécaniques, d'excellentes caractéristiques de résistance à la chaleur, d'excellentes caractéristiques chimiques et physiques et d'excellentes caractéristiques de moulage. L'invention concerne également : un procédé de fabrication efficace de la résine de polyamide copolymérisée pour moulage ; une composition de résine ; et un article moulé qui est formé à partir de la résine de polyamide copolymérisée pour moulage ou de la composition de résine.
PCT/JP2010/070858 2009-11-27 2010-11-24 Résine de polyamide copolymérisée, son procédé de fabrication, composition de résine et article moulé formé à partir de la résine de polyamide copolymérisée ou de la composition de résine WO2011065347A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US13/512,214 US8895690B2 (en) 2009-11-27 2010-11-24 Copolymerized polyamide resin, method for producing same, resin composition, and molded article formed from the copolymerized polyamide resin or the resin composition
PH1/2012/501041A PH12012501041A1 (en) 2009-11-27 2010-11-24 Copolymerized polyamide resin, method for producing same, resin composition, and molded article formed from the copolymerized polyamide resin or the resin composition
RU2012121824/04A RU2565069C2 (ru) 2009-11-27 2010-11-24 Сополимеризованная полиамидная смола, способ ее получения, смоляная композиция и формованное изделие, изготовленное из сополимеризованной полиамидной смолы или смоляной композиции
KR1020127013181A KR101845405B1 (ko) 2009-11-27 2010-11-24 공중합 폴리아미드 수지, 그 제조방법, 수지 조성물 및 이들로 이루어진 성형품
CN201080053801.4A CN102648232B (zh) 2009-11-27 2010-11-24 共聚聚酰胺树脂、其制造方法、树脂组合物和由它们形成的成型品
EP10833193.5A EP2505597B1 (fr) 2009-11-27 2010-11-24 Résine de polyamide copolymérisée, son procédé de fabrication, composition de résine et article moulé formé à partir de la résine de polyamide copolymérisée ou de la composition de résine
JP2011543253A JP5637144B2 (ja) 2009-11-27 2010-11-24 共重合ポリアミド樹脂、その製造方法、樹脂組成物およびそれらからなる成形品

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009-269762 2009-11-27
JP2009269760 2009-11-27
JP2009269762 2009-11-27
JP2009-269760 2009-11-27

Publications (1)

Publication Number Publication Date
WO2011065347A1 true WO2011065347A1 (fr) 2011-06-03

Family

ID=44066452

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/070858 WO2011065347A1 (fr) 2009-11-27 2010-11-24 Résine de polyamide copolymérisée, son procédé de fabrication, composition de résine et article moulé formé à partir de la résine de polyamide copolymérisée ou de la composition de résine

Country Status (10)

Country Link
US (1) US8895690B2 (fr)
EP (1) EP2505597B1 (fr)
JP (1) JP5637144B2 (fr)
KR (1) KR101845405B1 (fr)
CN (1) CN102648232B (fr)
MY (1) MY161840A (fr)
PH (1) PH12012501041A1 (fr)
RU (1) RU2565069C2 (fr)
TW (1) TWI580709B (fr)
WO (1) WO2011065347A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012070377A1 (fr) * 2010-11-26 2012-05-31 三菱瓦斯化学株式会社 Résine de polyamide et son procédé de moulage
US20130066041A1 (en) * 2010-07-27 2013-03-14 Mitsubishi Gas Chemical Company, Inc. Polyamide resin
WO2013129341A1 (fr) * 2012-02-28 2013-09-06 三菱瓦斯化学株式会社 Procédé de production de polyamide
WO2014073373A1 (fr) * 2012-11-08 2014-05-15 三菱瓦斯化学株式会社 Procédé de production de polyamide
KR101472071B1 (ko) 2012-02-28 2014-12-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리아미드의 제조방법
JP2016030820A (ja) * 2014-07-30 2016-03-07 三菱瓦斯化学株式会社 ポリアミドペレット及びその製造方法
JP2016124911A (ja) * 2014-12-26 2016-07-11 三菱エンジニアリングプラスチックス株式会社 ポリアミド樹脂組成物および成形品
JP2017110101A (ja) * 2015-12-16 2017-06-22 三菱瓦斯化学株式会社 ポリアミド樹脂および成形品
JP2017115093A (ja) * 2015-12-25 2017-06-29 三菱エンジニアリングプラスチックス株式会社 ポリアミド樹脂組成物、キット、成形品の製造方法、成形品およびポリアミド樹脂組成物の製造方法
JP7585735B2 (ja) 2020-11-20 2024-11-19 三菱瓦斯化学株式会社 樹脂組成物、成形体、および、ポリアミド樹脂の廃棄方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102554088B1 (ko) * 2015-05-27 2023-07-12 안헤우저-부시 인베브 에스.에이. 산소-포집 중합체 조성물
CN112646174B (zh) * 2019-12-27 2022-03-08 华润化学材料科技股份有限公司 一种共聚芳香-脂肪族半芳香尼龙及其制备方法
CN113185688A (zh) * 2021-03-31 2021-07-30 上海庚彩新材料科技有限公司 一种共聚酰胺及其制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4812390B1 (fr) 1968-07-23 1973-04-20
JPS5432458B2 (fr) 1974-11-26 1979-10-15
JPH0114925B2 (fr) 1981-06-04 1989-03-15 Mitsubishi Gas Chemical Co
JPH06207004A (ja) 1992-11-04 1994-07-26 Solvay & Cie ポリアミドの合成法
JPH0741670A (ja) 1993-07-27 1995-02-10 Mitsubishi Gas Chem Co Inc ポリアミド樹脂組成物
JPH07324130A (ja) 1994-04-07 1995-12-12 Mitsubishi Gas Chem Co Inc 共重合ポリアミドの製造法
JPH08259809A (ja) 1995-03-23 1996-10-08 Mitsubishi Gas Chem Co Inc ポリアミド樹脂組成物
JP2002060486A (ja) * 2000-08-24 2002-02-26 Mitsubishi Gas Chem Co Inc ポリアミドの製造方法
JP2007031475A (ja) * 2005-07-22 2007-02-08 Mitsubishi Gas Chem Co Inc ポリアミド樹脂
JP2007031630A (ja) * 2005-07-29 2007-02-08 Mitsubishi Gas Chem Co Inc ポリアミド樹脂
JP2008280535A (ja) * 2007-04-11 2008-11-20 Mitsubishi Gas Chem Co Inc ポリアミドの製造方法
JP2010007055A (ja) * 2008-05-29 2010-01-14 Mitsubishi Gas Chemical Co Inc ポリアミドの製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2399999A1 (fr) 1977-08-12 1979-03-09 Ici Ltd Carbamates ou esters de derives du 4-prostene-1-ol et composition pharmaceutique ou veterinaire les contenant
US5587447A (en) * 1994-04-07 1996-12-24 Mitsubishi Gas Chemical Co., Inc. Copolyamide production method
JPH0812390A (ja) 1994-06-22 1996-01-16 Sumitomo Metal Mining Co Ltd 人工軽量骨材の製造方法
JP3456501B2 (ja) * 1994-10-27 2003-10-14 三菱瓦斯化学株式会社 ポリアミド樹脂組成物
US6855755B1 (en) * 1999-08-04 2005-02-15 Mitsubishi Engineering-Plastics Corporation Polyamide resin composition having improved weathering resistance and its molded products
JP4168233B2 (ja) * 2002-05-10 2008-10-22 三菱瓦斯化学株式会社 ポリアミド製造法
US20050009976A1 (en) * 2003-07-10 2005-01-13 Honeywell International, Inc. Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles
US10273359B2 (en) * 2009-09-14 2019-04-30 Mitsubishi Gas Chemical Company, Inc. Polyamide resin composition

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4812390B1 (fr) 1968-07-23 1973-04-20
JPS5432458B2 (fr) 1974-11-26 1979-10-15
JPH0114925B2 (fr) 1981-06-04 1989-03-15 Mitsubishi Gas Chemical Co
JPH06207004A (ja) 1992-11-04 1994-07-26 Solvay & Cie ポリアミドの合成法
JPH0741670A (ja) 1993-07-27 1995-02-10 Mitsubishi Gas Chem Co Inc ポリアミド樹脂組成物
JPH07324130A (ja) 1994-04-07 1995-12-12 Mitsubishi Gas Chem Co Inc 共重合ポリアミドの製造法
JPH08259809A (ja) 1995-03-23 1996-10-08 Mitsubishi Gas Chem Co Inc ポリアミド樹脂組成物
JP2002060486A (ja) * 2000-08-24 2002-02-26 Mitsubishi Gas Chem Co Inc ポリアミドの製造方法
JP2007031475A (ja) * 2005-07-22 2007-02-08 Mitsubishi Gas Chem Co Inc ポリアミド樹脂
JP2007031630A (ja) * 2005-07-29 2007-02-08 Mitsubishi Gas Chem Co Inc ポリアミド樹脂
JP2008280535A (ja) * 2007-04-11 2008-11-20 Mitsubishi Gas Chem Co Inc ポリアミドの製造方法
JP2010007055A (ja) * 2008-05-29 2010-01-14 Mitsubishi Gas Chemical Co Inc ポリアミドの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2505597A4

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2011283795B2 (en) * 2010-07-27 2014-10-23 Mitsubishi Gas Chemical Company, Inc. Polyamide resin
US20130066041A1 (en) * 2010-07-27 2013-03-14 Mitsubishi Gas Chemical Company, Inc. Polyamide resin
US9163117B2 (en) * 2010-07-27 2015-10-20 Mitsubishi Gas Chemical Company, Inc. Polyamide resin
US8841407B2 (en) 2010-11-26 2014-09-23 Mitsubishi Gas Chemical Company, Inc. Polyamide resins and processes for molding them
WO2012070377A1 (fr) * 2010-11-26 2012-05-31 三菱瓦斯化学株式会社 Résine de polyamide et son procédé de moulage
WO2013129341A1 (fr) * 2012-02-28 2013-09-06 三菱瓦斯化学株式会社 Procédé de production de polyamide
US9359477B2 (en) 2012-02-28 2016-06-07 Mitsubishi Gas Chemical Company, Inc. Production method for polyamide
KR101472071B1 (ko) 2012-02-28 2014-12-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리아미드의 제조방법
KR20150082240A (ko) * 2012-11-08 2015-07-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리아미드의 제조방법
WO2014073373A1 (fr) * 2012-11-08 2014-05-15 三菱瓦斯化学株式会社 Procédé de production de polyamide
JPWO2014073373A1 (ja) * 2012-11-08 2016-09-08 三菱瓦斯化学株式会社 ポリアミドの製造方法
KR102091797B1 (ko) 2012-11-08 2020-03-20 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리아미드의 제조방법
JP2016030820A (ja) * 2014-07-30 2016-03-07 三菱瓦斯化学株式会社 ポリアミドペレット及びその製造方法
JP2016124911A (ja) * 2014-12-26 2016-07-11 三菱エンジニアリングプラスチックス株式会社 ポリアミド樹脂組成物および成形品
JP2017110101A (ja) * 2015-12-16 2017-06-22 三菱瓦斯化学株式会社 ポリアミド樹脂および成形品
JP2017115093A (ja) * 2015-12-25 2017-06-29 三菱エンジニアリングプラスチックス株式会社 ポリアミド樹脂組成物、キット、成形品の製造方法、成形品およびポリアミド樹脂組成物の製造方法
JP7585735B2 (ja) 2020-11-20 2024-11-19 三菱瓦斯化学株式会社 樹脂組成物、成形体、および、ポリアミド樹脂の廃棄方法

Also Published As

Publication number Publication date
US8895690B2 (en) 2014-11-25
RU2012121824A (ru) 2014-01-10
TW201129610A (en) 2011-09-01
KR101845405B1 (ko) 2018-04-05
TWI580709B (zh) 2017-05-01
EP2505597B1 (fr) 2017-11-15
EP2505597A1 (fr) 2012-10-03
JP5637144B2 (ja) 2014-12-10
PH12012501041A1 (en) 2016-05-25
MY161840A (en) 2017-05-15
US20120289643A1 (en) 2012-11-15
CN102648232B (zh) 2015-06-24
CN102648232A (zh) 2012-08-22
KR20120102056A (ko) 2012-09-17
JPWO2011065347A1 (ja) 2013-04-11
EP2505597A4 (fr) 2014-11-19
RU2565069C2 (ru) 2015-10-20

Similar Documents

Publication Publication Date Title
JP5637144B2 (ja) 共重合ポリアミド樹脂、その製造方法、樹脂組成物およびそれらからなる成形品
JP5664243B2 (ja) ポリアミド樹脂
JP5194978B2 (ja) ポリアミドの製造方法
US9260563B2 (en) Process for production of polyamide
JP2007321035A (ja) ポリアミド樹脂組成物
KR101601974B1 (ko) 폴리아미드의 제조방법
JP5470785B2 (ja) ポリアミド樹脂
WO2015115148A1 (fr) Procédé pour granuler un polyamide ou une composition de polyamide
JP5521297B2 (ja) ポリアミド樹脂
WO2014027651A1 (fr) Composition de polyéther polyamide
JP5700177B1 (ja) キシリレンジアミン組成物及びポリアミド樹脂の製造方法
JP2012149238A (ja) 半芳香族ポリアミド原料の製造方法および半芳香族ポリアミドの製造方法
WO2015064627A1 (fr) Composition de xylylène diamine et procédé de production d'un résine polyamide
TW201522284A (zh) 亞二甲苯二胺組成物及聚醯胺樹脂之製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080053801.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10833193

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011543253

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20127013181

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 4645/CHENP/2012

Country of ref document: IN

Ref document number: 12012501041

Country of ref document: PH

WWE Wipo information: entry into national phase

Ref document number: 1201002415

Country of ref document: TH

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2010833193

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2010833193

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13512214

Country of ref document: US

Ref document number: 2012121824

Country of ref document: RU